Liquid phase alkylation process

ABSTRACT

The present invention provides an improved process for conversion of feedstock comprising an alkylatable aromatic compound and an alkylating agent to desired alkylaromatic conversion product under at least partial liquid phase conversion conditions in the presence of specific catalyst comprising a porous crystalline material, e.g. a crystalline aluminosilicate, and binder in the ratio of crystal/binder of from about 20/80 to about 60/40. The porous crystalline material of the catalyst may comprise a crystalline molecular sieve having the structure of Beta, an MCM-22 family material, e.g. MCM-49, or a mixture thereof.

BACKGROUND OF THE INVENTION

The present invention relates to an improved process for producingalkylaromatics, for example, ethylbenzene, cumene and sec-butylbenzene.

Of the alkylaromatic compounds advantageously produced by the presentimproved process, ethylbenzene and cumene, for example, are valuablecommodity chemicals which are used industrially for the production ofstyrene monomer and coproduction of phenol and acetone respectively. Infact, a common route for the production of phenol comprises a processwhich involves alkylation of benzene with propylene to produce cumene,followed by oxidation of the cumene to the corresponding hydroperoxide,and then cleavage of the hydroperoxide to produce equimolar amounts ofphenol and acetone. Ethylbenzene may be produced by a number ofdifferent chemical processes. One process which has achieved asignificant degree of commercial success is the vapor phase alkylationof benzene with ethylene in the presence of a solid, acidic ZSM-5zeolite catalyst. Examples of such ethylbenzene production processes aredescribed in U.S. Pat. Nos. 3,751,504 (Keown), 4,547,605 (Kresge) and4,016,218 (Haag).

Another process which has achieved significant commercial success is theliquid phase process for producing ethylbenzene from benzene andethylene since it operates at a lower temperature than the vapor phasecounterpart and hence tends to result in lower yields of by-products.For example, U.S. Pat. No. 4,891,458 (Innes) describes the liquid phasesynthesis of ethylbenzene with zeolite beta, whereas U.S. Pat. No.5,334,795 (Chu) describes the use of MCM-22 in the liquid phasesynthesis of ethylbenzene. The latter patent teaches use of catalystcomprising MCM-22 crystalline material and binder in the ratio ofcrystal/binder of from about 1/99 to about 90/10.

Cumene has for many years been produced commercially by the liquid phasealkylation of benzene with propylene over a Friedel-Craft catalyst,particularly solid phosphoric acid or aluminum chloride. More recently,however, zeolite-based catalyst systems have been found to be moreactive and selective for propylation of benzene to cumene. For example,U.S. Pat. No. 4,992,606 (Kushnerick) describes the use of MCM-22 in theliquid phase alkylation of benzene with propylene.

Other publications show use of catalysts comprising crystalline zeolitesand binders for conversion of feedstock comprising an alkylatablearomatic compound and an alkylating agent to alkylaromatic conversionproduct under at least partial liquid phase conversion conditions. Theseinclude U.S. 2005/0197517A1 (Cheng) showing use of a catalystcrystal/binder ratio of 65/35 and 100/0; U.S. 2002/0137977A1(Hendriksen) showing use of a catalyst crystal/binder ratio of 100/0while noting the perceived negative effect of binders on selectivity;U.S. 2004/0138051A1 (Shan) showing use of a catalyst comprising amicroporous zeolite embedded in a mesoporous support, where thezeolite/support ratio is from less than 1/99 to more than 99/1,preferably from 3/97 to 90/10; WO 2006/002805 (Spano) teaching use of acatalyst crystal/binder ratio of 20/80 to 95/5, exemplifying 55/45; U.S.Pat. No. 6,376,730 (Jan) showing use of layered catalyst crystal/binderof 70/30 and 83/17; EP 0847802B1 showing use of a catalystcrystal/binder ratio of from 50/50 to 95/5, preferably from 70/30 to90/10; and U.S. Pat. No. 5,600,050 (Huang) showing use of catalystcomprising 30 to 70 wt. % H-Beta zeolite, 0.5 to 10 wt. % halogen, andthe remainder alumina binder.

Existing alkylation processes for producing alkylaromatic compounds, forexample, ethylbenzene and cumene, inherently produce polyalkylatedspecies as well as the desired monoalkylated product. It is thereforenormal to transalkylate the polyalkylated species with additionalaromatic feed, for example benzene, to produce additional monoalkylatedproduct, for example ethylbenzene or cumene, either by recycling thepolyalkylated species to the alkylation reactor or, more frequently, byfeeding the polyalkylated species to a separate transalkylation reactor.Examples of catalysts which have been used in the alkylation of aromaticspecies, such as alkylation of benzene with ethylene or propylene, andin the transalkylation of polyalkylated species, such aspolyethylbenzenes and polyisopropylbenzenes, are listed in U.S. Pat. No.5,557,024 (Cheng) and include MCM-49, MCM-22, PSH-3, SSZ-25, zeolite X,zeolite Y, zeolite Beta, acid dealuminized mordenite and TEA-mordenite.Transalkylation over a small crystal (<0.5 micron) form of TEA-mordeniteis also disclosed in U.S. Pat. No. 6,984,764.

Where the alkylation step is performed in the liquid phase, it is alsodesirable to conduct the transalkylation step under liquid phaseconditions. However, by operating at relatively low temperatures, liquidphase processes impose increased requirements on the catalyst,particularly in the transalkylation step where the bulky polyalkylatedspecies must be converted to additional monoalkylated product withoutproducing unwanted by-products. This has proven to be a significantproblem in the case of cumene production where existing catalysts haveeither lacked the desired activity or have resulted in the production ofsignificant quantities of by-products such as ethylbenzene andn-propylbenzene.

Although it is suggested in the art that catalysts for conversion offeedstock comprising an alkylatable aromatic compound and an alkylatingagent to alkylaromatic conversion product under at least partial liquidphase conversion conditions are composed of a porous crystallinealuminosilicate and binder in the ratio of crystal/binder of from 1/99,e.g. 5/95, to 100/0, current commercial catalysts, i.e. those found tobe commercially useful, for this process are composed of a porouscrystalline aluminosilicate and binder in the ratio of crystal/binder ofeither 65/35 or 80/20. Finding a commercially acceptable catalyst forsuch processes conducted under at lease partial liquid phase conversionconditions which increases monoselectivity, i.e. lower di- or polyalkylproduct make, would allow capacity expansion in existing plants andlower capital expense for grassroots plants as a result of loweraromatic compound/alkylating agent ratios. According to the presentinvention, it has now unexpectedly been found that a liquid phase orpartial liquid phase alkylation process for producing alkylaromaticsconducted in the presence of a specific catalyst comprising a porouscrystalline material, e.g. a crystalline aluminosilicate, (“crystal”)and binder in the ratio of crystal/binder of from about 20/80 to about60/40, yields a unique combination of activity and, importantly,monoselectivity. This is especially the case when the process involvesat least partial liquid phase alkylation for manufacture of ethylbenzeneor cumene. This obviates or lessens the demand in many instances for thedifficult transalkylation reaction for conversion of unwanted bulkypolyalkylated species in such a process.

SUMMARY OF THE INVENTION

According to the present invention, there is provided an improvedprocess for conversion of a feedstock comprising an alkylatable aromaticcompound and an alkylating agent to desired alkylaromatic conversionproduct under at least partial liquid phase conversion conditions in thepresence of specific catalyst comprising a porous crystalline material,e.g. a crystalline aluminosilicate, and binder in the ratio ofcrystal/binder of from about 20/80 to about 60/40. According to oneaspect of the invention, there is provided a process for selectivelyproducing a desired monoalkylated aromatic compound comprising the stepof contacting an alkylatable aromatic compound with an alkylating agentin the presence of catalyst under at least partial liquid phaseconditions, said catalyst comprising a porous crystalline material, e.g.a crystalline aluminosilicate, and binder in the ratio of crystal/binderof from about 20/80 to about 60/40. Another aspect of the presentinvention is an improved alkylation process for the selective productionof monoalkyl benzene comprising the step of reacting benzene with analkylating agent under alkylation conditions in the presence ofalkylation catalyst which comprises a porous crystalline material, e.g.a crystalline aluminosilicate, and binder in the ratio of crystal/binderof from about 20/80 to about 60/40.

The catalyst for use in the present process may comprise, for example, acrystalline molecular sieve having the structure of zeolite Beta, or onehaving an X-ray diffraction pattern including d-spacing maxima at12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms. Moreparticularly, the catalyst for use herein may comprise a crystallinemolecular sieve having the structure of Beta, an MCM-22 family material,e.g. MCM-22, or a mixture thereof.

The catalyst for use in the present invention preferably comprises anMCM-22 family material, such as for example a crystalline silicatehaving the structure of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2,ITQ-30, MCM-36, MCM-49, MCM-56, UZM-8 and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an improved process for production ofmonoalkylated aromatic compounds, particularly ethylbenzene, cumene andsec-butylbenzene, by the liquid or partial liquid phase alkylation of analkylatable aromatic compound, particularly benzene. More particularly,the present process uses a catalyst composition comprising a porouscrystalline material, e.g. a crystalline aluminosilicate, and binder inthe ratio of crystal/binder of from about 20/80 to about 60/40.

Methods for producing the catalysts required for use in the presentinvention comprise those taught in the publications listed below andincorporated herein by reference, modified only by adjusting thecompounding or extrusion, for example, of the final catalyst to comprisea crystal/binder ratio of from about 20/80 to about 60/40. This is wellwithin the ability of those skilled in catalyst manufacturing art. Forexample, U.S. Pat. No. 4,954,325 describes crystalline MCM-22 andcatalyst comprising same, U.S. Pat. No. 5,236,575 describes crystallineMCM-49 and catalyst comprising same, and U.S. Pat. No. 5,362,697describes crystalline MCM-56 and catalyst comprising same. Incompounding or extruding the particular crystalline material with binderto form the catalyst required for use herein, care is taken to do sosuch that the final catalyst product comprises a crystal/binder ratio offrom about 20/80 to about 60/40.

The term “aromatic” in reference to the alkylatable aromatic compoundswhich may be useful as feedstock herein is to be understood inaccordance with its art-recognized scope. This includes alkylsubstituted and unsubstituted mono- and polynuclear compounds. Compoundsof an aromatic character that possess a heteroatom are also usefulprovided they do not act as catalyst poisons under the reactionconditions selected.

Substituted aromatic compounds that can be alkylated herein must possessat least one hydrogen atom directly bonded to the aromatic nucleus. Thearomatic rings can be substituted with one or more alkyl, aryl, alkaryl,alkoxy, aryloxy, cycloalkyl, halide, and/or other groups that do notinterfere with the alkylation reaction.

Suitable aromatic compounds include benzene, naphthalene, anthracene,naphthacene, perylene, coronene, and phenanthrene, with benzene beingpreferred.

Generally the alkyl groups that can be present as substituents on thearomatic compound contain from 1 to about 22 carbon atoms and usuallyfrom about 1 to 8 carbon atoms, and most usually from about 1 to 4carbon atoms.

Suitable alkyl substituted aromatic compounds include toluene, xylene,isopropylbenzene, n-propylbenzene, alpha-methylnaphthalene,ethylbenzene, mesitylene, durene, cymenes, butylbenzene, pseudocumene,o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene,isohexylbenzene, pentaethylbenzene, pentamethylbenzene;1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene;1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene;p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene;m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalenes;ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene;2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; and3-methyl-phenanthrene. Higher molecular weight alkylaromatic compoundscan also be used as starting materials and include aromatic organicssuch as are produced by the alkylation of aromatic organics with olefinoligomers. Such products are frequently referred to in the art asalkylate and include hexylbenzene, nonylbenzene, dodecylbenzene,pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene,pentadecytoluene, etc. Very often alkylate is obtained as a high boilingfraction in which the alkyl group attached to the aromatic nucleusvaries in size from about C₆ to about C₁₂. When cumene or ethylbenzeneis the desired product, the present process produces acceptably littleby-products such as xylenes. The xylenes made in such instances may beless than about 500 ppm.

Reformate containing a mixture of benzene, toluene and/or xyleneconstitutes a particularly useful feed for the alkylation process ofthis invention.

The alkylating agents that may be useful in the process of thisinvention generally include any aliphatic or aromatic organic compoundhaving one or more available alkylating aliphatic groups capable ofreaction with the alkylatable aromatic compound, preferably with thealkylating group possessing from 1 to 5 carbon atoms. Examples ofsuitable alkylating agents are olefins such as ethylene, propylene, thebutenes, and the pentenes; alcohols (inclusive of monoalcohols,dialcohols, trialcohols, etc.) such as methanol, ethanol, the propanols,the butanols, and the pentanols; aldehydes such as formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, and n-valeraldehyde; andalkyl halides such as methyl chloride, ethyl chloride, the propylchlorides, the butyl chlorides, and the pentyl chlorides, and so forth.

Mixtures of light olefins are useful as alkylating agents in thealkylation process of this invention. Accordingly, mixtures of ethylene,propylene, butenes, and/or pentenes which are major constituents of avariety of refinery streams, e.g., fuel gas, gas plant off-gascontaining ethylene, propylene, etc., naphtha cracker off-gas containinglight olefins, refinery FCC propane/propylene streams, etc., are usefulalkylating agents herein. For example, a typical FCC light olefin streampossesses the following composition:

Wt. % Mole % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32Pentanes 0.7 0.4

Reaction products that may be obtained from the process of the presentinvention include ethylbenzene from the reaction of benzene withethylene, cumene from the reaction of benzene with propylene,ethyltoluene from the reaction of toluene with ethylene, cymenes fromthe reaction of toluene with propylene, and sec-butylbenzene from thereaction of benzene and n-butene. Particularly preferred processmechanisms of the invention relate to the production of cumene by thealkylation of benzene with propylene, and production of ethylbenzene bythe alkylation of benzene with ethylene.

The reactants for the present improved process can be in partially orcompletely liquid phase and can be neat, i.e. free from intentionaladmixture or MWW topology are multi-layered materials which have twopore systems arising from the presence of both 10 and 12 membered rings.The Atlas of Zeolite Framework Types classes five differently namedmaterials as having this same topology: MCM-22, ERB-1, ITQ-1, PSH-3, andSSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a monoalkylated aromatic compound, particularly cumene,comprising the step of contacting a polyalkylated aromatic compound withan alkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe monoalkylated aromatic compound, wherein the transalkylationcatalyst comprises a mixture of at least two different crystallinemolecular sieves, wherein each of the molecular sieves is selected fromzeolite beta, zeolite Y, mordenite and a material having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms.

In the reaction mechanism of the present invention, the alkylationreactor effluent may contain excess aromatic feed, monoalkylatedproduct, polyalkylated products, and various impurities. The aromaticfeed is recovered by distillation and recycled to the alkylationreactor. Usually a small bleed is taken from the recycle stream toeliminate unreactive impurities from the loop. The bottoms from thedistillation may be further distilled to separate monoalkylated productfrom polyalkylated products and other heavies.

The polyalkylated products separated from the alkylation reactoreffluent may be reacted with additional aromatic feed in atransalkylation reactor, separate from the alkylation reactor, over asuitable transalkylation catalyst. The transalkylation catalyst maycomprise one or a mixture of crystalline molecular sieves having thestructure of zeolite Beta, zeolite Y, mordenite or an MCM-22 familymaterial having an X-ray diffraction pattern including d-spacing maximaat 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms.

The X-ray diffraction data used to characterize said above catalyststructures are obtained by standard techniques using the K-alpha doubletof copper as the incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials having the above X-ray diffraction lines include, for example,MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S.Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667),ERB-1 (described in European Patent No. 0293032), ITQ-1 (described inU.S. Pat. No. 6,077,498), ITQ-2 (described in U.S. Pat. No. 6,231,751),ITQ-30 (described in WO 2005-118476), MCM-36 (described in U.S. Pat. No.5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575) and MCM-56(described in U.S. Pat. No. 5,362,697), with MCM-22 being particularlypreferred.

Zeolite Beta is disclosed in U.S. Pat. No. 3,308,069. Zeolite Y andmordenite occur naturally but may also be used in one of their syntheticforms, such as Ultrastable Y (USY), which is disclosed in U.S. Pat. No.3,449,070, Rare earth exchanged Y (REY), which is disclosed in U.S. Pat.No. 4,415,438, and TEA-mordenite (i.e., synthetic mordenite preparedfrom a reaction mixture comprising a tetraethylammonium directingagent), which is disclosed in U.S. Pat. Nos. 3,766,093 and 3,894,104.However, in the case of TEA-mordenite for use in the transalkylationcatalyst, the particular synthesis regimes described in the patentsnoted lead to the production of a mordenite product composed ofpredominantly large crystals with a size greater than 1 micron andtypically around 5 to 10 micron. It has been found that controlling thesynthesis so that the resultant TEA-mordenite has an average crystalsize of less than 0.5 micron results in a transalkylation catalyst withmaterially enhanced activity for liquid phase aromatics transalkylation.

The small crystal TEA-mordenite desired for transalkylation can beproduced by crystallization from a synthesis mixture having a molarcomposition within the following ranges:

Useful Preferred R/R+Na+ = >0.4  0.45-0.7  OH—/SiO2 = <0.22 0.05-0.2 Si/Al2 = >30-90 35-50 H2O/OH =   50-70 50-60

The crystallization of small crystal TEA-mordenite from this synthesismixture is conducted at a temperature of 90 to 200° C., for a time of 6to 180 hours.

The catalyst for use in the present invention will include an inorganicoxide material matrix or binder. Such matrix or binder materials includesynthetic or naturally occurring substances as well as inorganicmaterials such as clay, silica and/or metal oxides. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Naturally occurringclays which can be composited with the inorganic oxide material includethose of the montmorillonite and kaolin families, which families includethe subbentonites and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite or anauxite. Suchclays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.

Specific useful catalyst matrix or binder materials employed hereininclude silica, alumina, zirconia, titania, silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

For the improvement of the present invention, relative proportions ofthe crystalline molecular sieve and binder or matrix may vary narrowlywith the ratio of crystal/binder of from about 20/80 to about 60/40.

The catalyst for use in the present invention, or its crystallinemolecular sieve component, may or may not contain addedfunctionalization, such as, for example, a metal of Group VI (e.g. Crand Mo), Group VII (e.g. Mn and Re) or Group VIII (e.g. Co, Ni, Pd andPt), or phosphorus.

Non-limiting examples of the invention involving an improved alkylationmechanism are described with reference to the following experiments. Inthese experiments, catalyst reactivity was measured by the followingprocedure.

Equipment

A 300 ml Parr batch reaction vessel equipped with a stir rod and staticcatalyst basket was used for the activity and selectivity measurements.The reaction vessel was fitted with two removable vessels for theintroduction of benzene and propylene respectively.

Feed Pretreatment

Benzene

Benzene was obtained from a commercial source. The benzene was passedthrough a pretreatment vessel (2 L Hoke vessel) containing equal parts(by volume) molecular sieve 13×, molecular sieve 4A, Engelhard F-24Clay, and Selexsorb CD (in order from inlet to outlet). All feedpretreatment materials were dried in a 260° C. oven for 12 hours beforeusing.

Propylene

Propylene was obtained from a commercial specialty gases source and waspolymer grade. The propylene was passed through a 300 ml vesselcontaining pretreatment materials in the following order:

a. 150 ml molecular sieve 5A

b. 150 ml Selexsorb CD

Both guard-bed materials were dried in a 260° C. oven for 12 hoursbefore using.

Nitrogen

Nitrogen was ultra high purity grade and obtained from a commercialspecialty gases source. The nitrogen was passed through a 300 ml vesselcontaining pretreatment materials in the following order:

a. 150 ml molecular sieve 5A

b. 150 ml Selexsorb CD

Both guard-bed materials were dried in a 260° C. oven for 12 hoursbefore using.

Catalyst Preparation and Loading

A 2 gram sample of catalyst was dried in an oven in air at 260° C. for 2hours. The catalyst was removed from the oven and immediately 1 gram ofcatalyst was weighed. Quartz chips were used to line the bottom of abasket followed by loading of 0.5 or 1.0 gram of catalyst into thebasket on top of the first layer of quartz. Quartz chips were thenplaced on top of the catalyst. The basket containing the catalyst andquartz chips was placed in an oven at 260° C. overnight in air for about16 hours.

The reactor and all lines were cleaned with a suitable solvent (such astoluene) before each experiment. The reactor and all lines were dried inair after cleaning to remove all traces of cleaning solvent. The basketcontaining the catalyst and quartz chips was removed from the oven andimmediately placed in the reactor and the reactor was immediatelyassembled.

Test Sequence

The reactor temperature was set to 170° C. and purged with 100 sccm(standard cubic centimeter) of the ultra high purity nitrogen for 2hours. After nitrogen purged the reactor for 2 hours, the reactortemperature was reduced to 130° C., the nitrogen purge was discontinuedand the reactor vent closed. A 156.1 gram quantity of benzene was loadedinto a 300 ml transfer vessel, performed in a closed system. The benzenevessel was pressurized to 790 kPa-a (100 psig) with the ultra highpurity nitrogen and the benzene was transferred into the reactor. Theagitator speed was set to 500 rpm and the reactor was allowed toequilibrate for 1 hour. A 75 ml Hoke transfer vessel was then filledwith 28.1 grams of liquid propylene and connected to the reactor vessel,and then connected with 2169 kPa-a (300 psig) ultra high puritynitrogen. After the one-hour benzene stir time had elapsed, thepropylene was transferred from the Hoke vessel to the reactor. The 2169kPa-a (300 psig) nitrogen source was maintained connected to thepropylene vessel and open to the reactor during the entire run tomaintain constant reaction pressure during the test. Liquid productsamples were taken at 30, 60, 120, 150, 180 and 240 minutes afteraddition of the propylene.

In the Examples below, selectivity is the ratio of recovered productdiisopropylbenzene to recovered product isopropylbenzene (DIPB/IPB)after propylene conversion reached 100%. The activity of some examplesis determined by calculating the 2nd order rate constant usingmathematical techniques known to those skilled in the art.

EXAMPLE 1

Catalyst comprising MCM-49 and alumina binder in the crystal/binderratio of 80/20 was prepared by extrusion as a 1.27 mm ( 1/20th inch)quadrulobe extrudates.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 199. The selectivity(DIPB/IPB) was 16.4%.

EXAMPLE 2

Catalyst comprising MCM-49 and alumina binder in the crystal/binderratio of 60/40 was also prepared by extrusion as a 1.27 mm ( 1/20thinch) quadrulobe in the same manner as the catalyst for Example 1.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 236. The selectivity(DIPB/IPB) was 14.3%.

The process of Example 2 showed a 12.8% improvement in DIPB/IPBselectivity and an 18.6% improvement in activity relative to the parentprocess of Example 1.

EXAMPLE 3

Catalyst comprising MCM-49 and alumina binder in the crystal/binderratio of 40/60 was also prepared by extrusion as a 1.27 mm ( 1/20thinch) quadrulobe in the same manner as the catalyst for Example 1.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 106. The selectivity(DIPB/IPB) was 10.2%.

The process of Example 3 showed a 37.8% improvement in DIPB/IPBselectivity relative to the parent process of Example 1 while activityremained within 47% of that of the parent process.

EXAMPLE 4

Catalyst comprising MCM-49 and alumina binder in the crystal/binderratio of 20/80 was prepared by extrusion as a 1.27 mm ( 1/20th inch)quadrulobe extrudate in the same manner as the catalyst for Example 1.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 185. The selectivity(DIPB/IPB) was 8.6%.

The process of Example 4 showed an improvement in DIPB/IPB selectivityrelative to the parent process of Example 1 of 48%, while activityremained within about 1% of that of the parent.

EXAMPLE 5

Catalyst comprising self-bound MCM-22 (therefore a crystal/binder ratioof 100/0) was prepared by extrusion as a 1.59 mm ( 1/16th inch)cylindrical extrudate.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 295. The selectivity(DIPB/IPB) was 26.9%.

EXAMPLE 6

Catalyst comprising MCM-22 and alumina binder in the crystal/binderratio of 80/20 was prepared by extrusion as 1.59 mm ( 1/16th inch)cylindrical extrudate in the same manner as the catalyst for Example 5.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 184. The selectivity(DIPB/IPB) was 14.0%.

EXAMPLE 7

Catalyst comprising MCM-22 and alumina binder in the crystal/binderratio of 65/35 was prepared by extrusion as 1.59 mm ( 1/16th inch)cylindrical extrudate in the same manner as the catalyst for Example 5.

A 0.5 gram quantity of the catalyst of this example was placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). Activity determined bycalculating the 2nd order rate constant was 222. The selectivity(DIPB/IPB) was 13.7%.

EXAMPLE 8

Catalyst comprising MCM-22 and alumina binder in the crystal/binderratio of 60/40 is prepared by extrusion as 1.59 mm ( 1/16th inch)cylindrical extrudate in the same manner as the catalyst for Example 5.

A 0.5 gram quantity of the catalyst of this example is placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). The selectivity (DIPB/IPB) isabout 9.5%, an improvement of from about 31% to about 65% over theprocesses of Examples 5, 6 and 7.

EXAMPLE 9

Catalyst comprising MCM-22 and alumina binder in the crystal/binderratio of 40/60 is prepared by extrusion as 1.59 mm ( 1/16th inch)cylindrical extrudate in the same manner as the catalyst for Example 5.

A 0.5 gram quantity of the catalyst of this example is placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). The selectivity (DIPB/IPB) isabout 4.5%, an improvement of from about 67% to about 83% over theprocesses of Examples 5, 6 and 7.

EXAMPLE 10

Catalyst comprising MCM-22 and alumina binder in the crystal/binderratio of 20/80 is prepared by extrusion as 1.59 mm ( 1/16th inch)cylindrical extrudate in the same manner as the catalyst for Example 5.

A 0.5 gram quantity of the catalyst of this example is placed in thebatch reactor as described in the catalyst reactivity testing procedureabove at a 260° C. pretreatment temperature and contacted with 3 partsbenzene and 1 part propylene on a molar basis at a temperature of 130°C. and pressure of 2169 kPa-a (300 psig). The selectivity (DIPB/IPB) isabout 0.5%, an improvement of from about 96% to about 98% over theprocesses of Examples 5, 6 and 7.

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and may be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

1. In a process for alkylation of feedstock comprising at least onealkylatable aromatic compound and an alkylating agent to an alkylationproduct comprising an alkylaromatic compound which comprises contactingsaid feedstock in at least partial liquid phase under catalyticalkylation conditions including a temperature of from about 0° C. toabout 500° C., a pressure of from about 20 to about 25000 kPa-a, a molarratio of alkylatable aromatic compound to alkylating agent of from about0.1:1 to about 50:1, and a feed weight hourly space velocity (WHSV)based on the alkylating agent of from about 0.1 to about 500 hr⁻¹, witha catalyst composition comprising crystalline MCM-22 or MCM-49 zeoliteand an alumina binder having a ratio of crystal/binder of from about20/80 to about 60/40; wherein the dialkylbenzene to monoalkylbenzeneselectivity is less than about 14%.
 2. The process of claim 1 whereinsaid alkylation conditions include a temperature of from about 10° C. toabout 260° C., a pressure of from about 100 kPa-a to about 5500 kPa-a, amolar ratio of alkylatable aromatic compound to alkylating agent of fromabout 0.5:1 to about 10:1, and a feed weight hourly space velocity(WHSV) based on the alkylating agent of from about 0.5 to about 100hr⁻¹.
 3. The process of claim 1 wherein said feedstock comprisesreformate.
 4. The process of claim 1 wherein said feedstock aromaticcompound is benzene and said alkylating agent is selected from the groupconsisting of ethylene, propylene and butenes.
 5. The process of claim 1wherein said feedstock aromatic compound is benzene and said alkylatingagent is ethylene, said alkylation product comprises ethylbenzene, andsaid alkylation conditions include a temperature of from about 150° C.to about 300° C., a pressure up to about 20400 kPa-a, a weight hourlyspace velocity (WHSV) based on the ethylene alkylating agent of fromabout 0.1 to about 20 hr⁻¹, and a ratio of benzene to ethylene in thealkylation reactor of from about 0.5:1 to about 30:1 molar.
 6. Theprocess of claim 1 wherein said feedstock aromatic compound is benzeneand said alkylating agent is propylene, said alkylation productcomprises cumene, and said alkylation conditions include a temperatureof up to about 250° C., a pressure of about 25000 kPa-a or less, aweight hourly space velocity (WHSV) based on propylene alkylating agentof from about 0.1 hr⁻¹ to about 250 hr⁻¹, and a ratio of benzene topropylene in the alkylation reactor of from about 0.5:1 to about 30:1molar.
 7. The process of claim 1 wherein said feedstock aromaticcompound is benzene and said alkylating agent is butenes, saidalkylation product comprises butylbenzene, and said alkylationconditions include a temperature of up to about 250° C., a pressure ofabout 25000 kPa-a or less, a weight hourly space velocity (WHSV) basedon butenes alkylating agent of from about 0.1 hr⁻¹ to about 250 hr⁻¹,and a ratio of benzene to butenes in the alkylation reactor of fromabout 0.5:1 to about 30:1 molar.